Chromium titration

The precision of the colorimetric method is slightly poorer than that for the chromium titration-based procedure. Nevertheless, in other investigations it has been indicated that this method affords precision values up to seven times better than the opened reflux method [37]. 

BackTitrations. In the performance of aback titration, a known, but excess quantity of EDTA or other chelon is added, the pH is now properly adjusted, and the excess of the chelon is titrated with a suitable standard metal salt solution. Back titration procedures are especially useful when the metal ion to be determined cannot be kept in solution under the titration conditions or where the reaction of the metal ion with the chelon occurs too slowly to permit a direct titration, as in the titration of chromium(III) with EDTA. Back titration procedures sometimes permit a metal ion to be determined by the use of a metal indicator that is blocked by that ion in a direct titration. Eor example, nickel, cobalt, or aluminum form such stable complexes with Eriochrome Black T that the direct titration would fail. However, if an excess of EDTA is added before the indicator, no blocking occurs in the back titration with a magnesium or zinc salt solution. These metal ion titrants are chosen because they form EDTA complexes of relatively low stability, thereby avoiding the possible titration of EDTA bound by the sample metal ion. 

In this titration the analyte is oxidized from Fe + to Fe +, and the titrant is reduced from CryOy to Cr +. Oxidation of Fe + requires only a single electron. Reducing CryOy, in which chromium is in the +6 oxidation state, requires a total of six electrons. Conservation of electrons for the redox reaction, therefore, requires that... 

Wet-Chemical Determinations. Both water-soluble and prepared insoluble samples must be treated to ensure that all the chromium is present as Cr(VI). For water-soluble Cr(III) compounds, the oxidation is easily accompHshed using dilute sodium hydroxide, dilute hydrogen peroxide, and heat. Any excess peroxide can be destroyed by adding a catalyst and boiling the alkaline solution for a short time (101). Appropriate ahquot portions of the samples are acidified and chromium is found by titration either using a standard ferrous solution or a standard thiosulfate solution after addition of potassium iodide to generate an iodine equivalent. The ferrous endpoint is found either potentiometricaHy or by visual indicators, such as ferroin, a complex of iron(II) and o-phenanthroline, and the thiosulfate endpoint is ascertained using starch as an indicator. 

To determine moderate amounts of Cr(III) and Cr(VI) in samples that have both oxidation states present, Cr(VI) is analyzed by direct titration in one sample, and the total chromium is found in a second sample after oxidation of the Cr(III). The Cr(III) concentration is determined as the difference. Trace quantities of Cr(VI) in Cr(III) compounds can be detected and analyzed by (3)-diphenylcarbazide. Trace quantities of Cr(III) in Cr(VI) may be detected and analyzed either photometrically (102) or by ion chromatography using various modes of detection (103). 

When a solution of chromic and sulfuric acids in water is added at 0-20° to an alcohol or formate dissolved in acetone, a rapid oxidation takes place with the separation of the green chromium III reduction product as a separate layer. This system is commonly known as Jones reagent. The rate of oxidation is so fast that it is often possible to run the reaction as a titration to an... 

Iron (and nickel, if present) can be determined by adding an excess of standard EDTA to the cold solution, and then back-titrating the solution with lead nitrate solution using xylenol orange as indicator provided the solution is kept cold, chromium does not react. The solution from the back-titration is then acidified, excess of standard EDTA solution added and the solution boiled for 15 minutes when the red-violet Cr(III)-EDTA complex is produced. After cooling and buffering to pH 6, the excess EDTA is then titrated with the lead nitrate solution. 

The first titration determines the amount of EDTA used by the iron, and the second, the amount of EDTA used by the chromium. 

It is possible to titrate two substances by the same titrant provided that the standard potentials of the substances being titrated, and their oxidation or reduction products, differ by about 0.2 V. Stepwise titration curves are obtained in the titration of mixtures or of substances having several oxidation states. Thus the titration of a solution containing Cr(VI), Fe(III) and V(V) by an acid titanium(III) chloride solution is an example of such a mixture in the first step Cr(VI) is reduced to Cr(III) and V(V) to V(IV) in the second step Fe(III) is reduced to Fe(II) in the third step V(IV) is reduced to V(III) chromium is evaluated by difference of the volumes of titrant used in the first and third steps. Another example is the titration of a mixture of Fe(II) and V(IV) sulphates with Ce(IV) sulphate in dilute sulphuric acid in the first step Fe(II) is oxidised to Fe(III) and in the second jump V(IV) is oxidised to V(V) the latter change is accelerated by heating the solution after oxidation of the Fe(II) ion is complete. The titration of a substance having several oxidation states is exemplified by the stepwise reduction by acid chromium(II) chloride of Cu(II) ion to the Cu(I) state and then to the metal. 

Discussion. Chromium (III) salts are oxidised to dichromate by boiling with excess of a persulphate solution in the presence of a little silver nitrate (catalyst). The excess of persulphate remaining after the oxidation is complete is destroyed by boiling the solution for a short time. The dichromate content of the resultant solution is determined by the addition of excess of a standard iron(II) solution and titration of the excess of the latter with standard 0.02 M potassium dichromate. 

Procedure. Weigh out accurately an amount of the salt which will contain about 0.25 g of chromium, and dissolve it in 50 mL distilled water. Add 20 mL of ca 0.1 M silver nitrate solution, followed by 50 mL of a 10 per cent solution of ammonium or potassium persulphate. Boil the liquid gently for 20 minutes. Cool, and dilute to 250 mL in a graduated flask. Remove 50 mL of the solution with a pipette, add 50 mL of a 0.1 M ammonium iron(II) sulphate solution (Section 10.97, Procedure A), 200 mL of 1M sulphuric acid, and 0.5 mL of /V-phenylanthranilic acid indicator. Titrate the excess of the iron(II) salt with standard 0.02M potassium dichromate until the colour changes from green to violet-red. 

This reaction is subject to a number of errors (1) the hydriodic acid (from excess of iodide and acid) is readily oxidised by air, especially in the presence of chromium(III) salts, and (2) it is not instantaneous. It is accordingly best to pass a current of carbon dioxide through the reaction flask before and during the titration (a more convenient but less efficient method is to add some solid sodium hydrogencarbonate to the acid solution, and to keep the flask covered as much as possible), and to allow 5 minutes for its completion. 

With the exception of iron(II) and uranium(IV), the reduced solutions are extremely unstable and readily re-oxidise upon exposure to air. They are best stabilised in a five-fold excess of a solution of 150g of ammonium iron(III) sulphate and 150 mL of concentrated sulphuric acid per litre [approximately 0.3M with respect to iron] contained in the filter flask. The iron(II) formed is then titrated with a standard solution of a suitable oxidising agent. Titanium and chromium are completely oxidised and produce an equivalent amount of iron(II) sulphate molybdenum is re-oxidised to the Mo(V) (red) stage, which is fairly stable in air, and complete oxidation is effected by the permanganate, but the net result is the same, viz. Mo(III)- Mo(VI) vanadium is re-oxidised to the V(IV), condition, which is stable in air, and the final oxidation is completed by slow titration with potassium permanganate solution or with cerium(IV) sulphate solution. 

The chromium in the substance is converted into chromate or dichromate by any of the usual methods. A platinum indicator electrode and a saturated calomel electrode are used. Place a known volume of the dichromate solution in the titration beaker, add 10 mL of 10 per cent sulphuric acid or hydrochloric acid per 100 mL of the final volume of the solution and also 2.5 mL of 10 per cent phosphorus) V) acid. Insert the electrodes, stir, and after adding 1 mL of a standard ammonium iron)II) sulphate solution, the e.m.f. is measured. Continue to add the iron solution, reading the e.m.f. after each addition, then plot the titration curve and determine the end point. 

Chromium. 25.0 mL chromium(III) ion solution (0.02M, prepared by dilution of stock solution) + 50.0 mL 0.02 M EDTA + 50mL acetate buffer, boiled for 10 minutes, solution cooled, pH adjusted to 4.6 with hexamine, 1 drop of mercury-EDTA solution added, and then back-titrated with standard zinc ion solution. 

The fluorine titration of chromium oxide was carried out at the Elf-Atochem Research Center, Pieire-Benite.The catalyst mineralization was carried out in a Parr bomb by reaction with sodium peroxyde. Fluorine ions were then titrated by a potentiometric method with a specific fluoride electrode. 

A slight excess of base may be titrated in the previous reactions to shift the pH to a slight basic condition. This is important for the precipitation of certain metal salts (such as nickel, iron, and trivalent chromium) as hydroxides. 

A redox titration is based on an oxidation-reduction reaction between analyte and titrant. In addition to the many common analytes in chemistry, biology, and environmental and materials science thai can be measured by redox titrations, exotic oxidation states of elements in uncommon materials such as superconductors and laser materials are measured by redox titrations. For example, chromium added to laser crystals to increase their efficiency is found in the common oxidation states +3 and +6, and the unusual +4 state. A redox titration is a good way to unravel the nature of this complex mixture of chromium ions. 

To measure the total oxidizing power of chromium in the material, a crystal was dissolved in 2.9 M HC104 at 100°C, cooled to 20°C, and titrated with standard Fe2+, using Pt and Ag AgCl electrodes to find the end point. Chromium oxidized above the +3 state should oxidize an equivalent amount of Fe2+ in this step. That is, Cr4+ would consume one Fez+, and each atom of Cr6+ in Cr20 - would consume three Fe2+ ... 

Quantitative Determination. — Dissolve 5 gm. of chromium trioxide in water and dilute to 500 cc. Introduce 10 cc. of this solution into a stoppered flask of about 400 cc. capacity, dilute with 100 cc. of water, and add 5 gm. of potassium iodide and 2 cc. of hydrochloric acid. Allow the mixture to stand for about ten minutes with frequent shaking, then dilute with 200 cc. of water, and titrate with decinormal sodium thiosulphate solution. 

This is a special case where the replacement of groups already coordinated to a cation by a new ligand is a slow process. In the case of chromium(III) this can be attributed to losses of ligand-field stabilization energy whether a five- or a seven-coordinate reaction intermediate is involved and the classical example is the slow reaction with EDTA at room temperature. This makes it possible to titrate a mixture with other metals (e.g. Fem) which react quickly without interference from Crm. 

Another 100 c.c. of the solution is treated with 5-10 c.c. of concentrated hydrochloric acid and 10 c.c. of potassium iodide]solution, the iodine liberated being titrated with standard sodium thiosulphate solution in presence of starch paste and from the result the chromium, oxide calculated. The alumina is then obtained by difference from the two determinations. 

The identity of various derivatives is established by periodate titrations (41). Hydrolysis of the acetonide diacetate 6 by sulfuric acid in the presence of 2,4-dinitrophenylhydrazine (DNP) gives a small yield of the 16-acetate 10 (/). Also typical of the series, but not shown in the schemes, the C-7 alcohol group of compound 6 is oxidized to a ketone by chromium trioxide in pyridine (48,49). 

Before a load of chromium-containing ore is purchased, an ore sample must be analyzed. During the analysis, all the chromium in the sample is reacted to produce the dichromate ion. It took 82 mL of an acidified solution containing a total of 27.49 mg Fe2+ to titrate the sample, (a) What is the balanced equation (b) What is the mass (g) of chromium in the sample ... 

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